Preparing purified mixtures of esters



Patented Oct. 7, 1947 an ES PAT ENT orricia PREPAERING PURIFIED'MIXTURES OF ESTERS .Michael.A...-Eitelman, Hamburg N. assignor to.

Allied Chemical & Dye Corporation, a..corpo.--

ration ofNew York Nani-airing; Application March-.1, 1941, SerialNo.381,413:

17 Claims.

alcohols. The products of condensationof the.

halogenated hydrocarbons and sodium acetate contain as impuritiesconsiderable quantities of unreacted hydrocarbon halides andconsiderable quantities of olefines formed during the course of thcondensation reactions by the splitting,

off of hydrogen halide from the hydrocarbon halides.

and the" ester product boil at sufficiently widely separatedtemperatures to permitseparation of.

impurities from the esters by'simple; distillation.

However; ifa similar process is applied to a mixture of hydrocarbonscontaining or more carbon atoms-permolecule; the esters "and impuritiesformed boil" at approximatelythe same temperatures or theirboilingrangesoverlap to a substantial extent in the composite product.Thus it becomes exceedingly difiicultif not impossible to separate theimpurities from the desired esters by distillation. If the impuremixture of esters is converted directly without purification into thecorresponding mixture of alcohols by saponification, the'impurities arestill present and their separation from the alcohols presents the sameproblem.

It is an object of this invention to provide a process for preparingalcohols from higher. hydrocarbons which doesnot involve the separationproblem presented by former processes and which leads to the: productionof mixtures of higher alcohols, which are substantially free-fromnon-alcoholic impurities;

In accordance with my invention a mixture of halogenatedhigher-hydrocarbons containing halogenated non-aromatic hydrocarbongroups is condensedwith asalt of: a monobasiccarboxylic acid containingnot less than 6 carbon atoms in itsmolecule; andae a flux a quantity offree monobasic carboxylic; acid containing not less than 6- carbon atomsin its molecule, thereby forming a mixture of esters; the mixture ofesters is separated from non-ester impurities by distillation and issubsequently converted to a corresponding mixture of-. alcohols;

By the term higher hydrocarbons as used in,

this application I mean hyrocarbons containing at least 10 carbon atomsper molecule. Mixturesv such. as commercial; kerosene and distillatesand distillation residues thereof are illustra-tive, of: such. higherhydrocarbon mixtures. They may comprise highly complex mixtures ofstraight andbranched chain aliphatic compoundsv and alicyclichydrocarbons, whichv may contain aromatic hydrocarbon substituents. Theymay be obtained by fractional distillation ofpetroleum or by fractionaldistillation of cracking, or. cracking and hydrogenation, products: ofpetroleum! or bituminousshales or by fractional distillation of:hydrogenated. Edeleanu extracts, hydrogenated: coal. tars,or-theircracking prod,- ucts.

I have found that by forming a mixture of esters of a monobasicvcarboxylic acid containing 6101. more. carbon atoms. as aforesaid, I amable,. by distillation, to remove substantially completely,- impurities,suchas unreacted halogen compounds and. olefines, without. substantialloss of. ester product.

This: advantage of my process is illustrated by the followingcomparison: A chlorinated kero seneboiling between. and C. at 8- mm.absolute; pressure. was condensed with sodium acetate'in the presence ofglacial acetic acid. as; solvent. The reaction mixture was fractionallydistilledandthe fraction which boiled in the temperature range: from. to(3., at 8 mm. absolute pressure, andwhich contained the esters. ofacetic acid, was separately recovered. This fraction'contained 49%-of-esters, the' balance= consisting of impurities notseparable byordinary fractional distillation from the esters. If thefraction ishydrolyzed, the resulting mixture. of; alcohols likewise is not.separablefrom these: impurities by ordinaryf'ractional distillation.

Whencondensed' with sodium' benzoate in the presenceiof benzoic acid,the same kerosene chlo ride yielded a mixture from which, by fractionaldistillation, anester fraction was obtained which boiled in.thetemperature range from 2I5 to 250 C. at 51mm; absolute pressure, andcontained over 86% of esters. Thus, although a markedly broader cut wasmade in the case of thebenzoate- (a 35 cut ascompared with a. 20

cut), the ratio. of esters to impurities in this cut-was aboutisix timesthelratio in the-acetate product.

The halogenated! hydrocarbons may containas thehalogenfiuorine,chlorine; bromine, or iodine. The salts used for condensation with thehalogenated hydrocarbons include alkalimetal; alkaline earthmetal; andheavy metal salts. of aliphatic and: aromatic monocarboxylic acids;Examples of such salts are sodium benv zo.ate,: sodium. stearate, sodiumsalicylate; po-

tassium benzoate; silverbenzoate, calcium bennoleate, etc. Mixtures oftwo or more salts of difierent acids may be used.

2,428,450 If T 5' After the formation and purification of the W mixturesof esters, the latter are hydrolyzed by any conventional procedure tothe corresponding mixtures of alcohols.

The alcohol mixtures obtained by the process of the present inventionare useful as general solvents and as raw materials for manufacture ofesters, such as the phthalic acid esters, useful as plasticizers forcellulose esters; they are also valuable as intermediates for preparinginorganic and organic acid partial esters, such as acid sulfuric estersand salts thereof, which are valuable as wetting, dispersing andcleaning agents.

' A halogenated hydrocarbon mixture suitable for the purposes of theinvention may be prepared as follows: 7

A kerosene fraction comprising a mixture of hydrocarbons containingbetween 12 and 19 carbon atoms, inclusive, per molecule as determined,

for example, by a comparison of the boiling range thereof with theboiling ranges of hydrocarbons of known average molecular carboncontent, is chlorinated until the organically bound chlorine in themixture corresponds approximately to the amount which theoreticallywould be present if every hydrocarbon in the mixture weremonochlorinated.

Such a chlorinated hydrocarbon mixture is preferably fractionallydistilled to separate the portion which consists chiefly ofmonochlorinated hydrocarbons from unreacted hydrocarbons andpolychlorinated hydrocarbons, and the separated monochlor hydrocarbonportion is subjected to the process of this invention, preferably afollows: a

The, chlorinated hydrocarbon mixture is heated with slightly less thanits molecularly equivalent amount of the sodium salt of a carboxylicacid containing not less than 6 carbon atoms and, in addition,sufiicient of the free acid to render the reaction mass fluid underreaction conditions.

Conditions, such as press'ure,'are maintained so that reactants are notlost from the reaction vessel by evaporation. The time of heating andthe temperature of the reaction mixture are selected so as to strike anoptimum balance between two factors: (1) the greater tendency towardcompleteness of reaction at higher temperatures and with prolongedheating periods, and (2) the several hours with an excess of alcoholiccaustic I soda, whereby the alcoholic components are set free and may beseparated from the reaction mixture by fractional distillation.

Halogenated kerosene fractions having an av- ,erage molecular carboncontent between 12 and 719 are preferred because of their cheapnes andgreater tendency toward decomposition of'prodnot and of thechlorinatedhydrocarbon observed 1 when the reaction mixture is heated to hightemperatures and for long periods. reaction proceeds satisfactorilybetween about 150 C. and about 2'75. C, and the optimum combination oftime and temperature is about two Generally the hours'at 200 to 250 C.,but particular conditions depend upon the particular reaction.

As reaction flux or solvent there is used a free monobasic carboxylicacid which contains not less than 6 carbon atom in the molecule; butpreferably the acid used corresponds to the carboxylic acid salt whichis being condensed. This flux is used'in amount at least equal to theweight of the sodium salt.

The mixture is then fractionally distilled at about 10 mm. absolutepressure whereby there can be obtained in good yield a fractionconsisting of the esters of the carboxylic acid employed in thecondensation, which fraction is substantially free from unsaturated andchlorinated hydrocarbons. This fraction is then hydrolyzed by anystandard method, such as by refluxing for because on treating them inaccordance with this invention they yield alcohols which areparticularly valuable solvents, and the sulfuric acid derivatives ofwhich are highly useful detergents and wetting agents.

Chlorinated products are preferred to other halogenated products becauseof their cheapness, their ease ofpreparation', and as compared withbrominated and iodinated products, their some.

what higher vapor pressure.

The sodium salt is preferred since it affords the optimum combination.ore cheap alkali and ease of preparation in the anhydrous form.

A slight excess of chlorinated hydrocarbon result in greater smoothnessof reactio and increased yield,

. It is preferable to employ as flux or solvent the free acidcorresponding to the carboxylic acid salt being condensed because theyield is thereby increased. r r r The specific examples set forth belowillustrate how this invention can be carried out. Quantities areexpressed as parts by weight.

Example 1.'-A fraction of kerosene which was derived from Pennsylvaniapetroleum and had a boilin range of to C. at 10mm. absolute pressure andconsisted primarily of 15, 16, 1'7

and 18 carbon atom hydrocarbons, was chlorin-' ated with a direct streamof gaseous'chlorine in the presence of diffused sunlight until theincrease in weight of the chlorinated mixture, because of organicallycombined chlorine therein, amounted to about 13%. It was chiefly amixture of'unchlorinated hydrocarbons, monochlorinated hydrocarbons, anddichlorinated hydrocarbons with an average molecular carbon contentbetween 17 and 18 carbon atoms.

50 parts of benzoic acid and 25 parts of sodium benzoate were meltedtogether and to the agitated mixture 50 parts of the foregoing mixtureof chlorinated hydrocarbons were added. .The reacting mass wasmaintained at a temperature between 230 and 240 C. for about 2 hours andthen distilled in vacuo. The fraction which distilled off betWeen215 and250 C. at 5 mm. absolute pressure was collectedseparately. It consistedof a neutral viscous oil, insoluble in water and warm dilute aqueouscaustic soda, and comprised about 86% kerosene'benzoate (the keroseneradicals having an average carbon content betweenl'? and 18 carbonatoms).

30 parts of the ester product were mixed with a 36 parts of a 10% (byweight) alcoholic solution of caustic soda and the whole was stirred andheated under reflux at atmospheric pressure for about 2 hours. At theend of this time, the

reacting mass was diluted with 200 parts of water,

F5 '.carbon .;content P-between .317 and i1' 8 eatoms mer imolecule.

Example .;2. -A :straighterun idrerosene ifrcm -Rennsylvania :spetroleum:nwas .rlistilled, :and :the

idi'stil-latedistilling overizinithe":temperaturerrange 'rfrom;ll8.ftol3l C..;at..

was then .idistilled .in yacuo, and :the fraction 1;

which idistilled'ofi ibetweeni 196:a-nd. .2 1810; at 1 .mm; absolutepressure 11w.as:.col=lectedz separately. The fraction consisted:of.:a=:neutral- .oil which was :insoluble in watera-andrin warm--aquecus-:caustic soda: and consisted. of 99% kerosene .benzease.

Azportionofthe .oil wast-refluxed with about times its weight .;ofarnormal. alcoholic solution of; caustic .soda for .2 /2 :hours .toihydrolyze ethe kerosene 1benzoate. .zThe mixture..o-f..-1alcoholsrremoved from the hydrolyzedeproductvwas'aaeclearfpa-IQJYGHOWE liquid of,v sp gr. 15 =0.-84 5,z boiling from. 145 ,to.175.C. .at. 15;.mm. :absolute pressure. Example 3..'Kerosene which:wasderiyedzirom -.Pennsylvania petroleum, and had 'dbeen washed withconcentrated: sulfuric acidswas-:distilledand :the fractionboilinggbetweenil'lll" and 180 ;.C. at 5 .mm; absolutepressure:wascollected.separately :as a;mixture;;oi hydrocarbons.consisting :prima- 'rily of .19.and.20 carboneatom hydrocarbons. Thisdistilled kerosene :fraction was echlorinated directly with chlorine:gasin diffused tsunlightsiat aa;temperature:of about: .C.. until'thezo-rganica-lly combined chlorine in' the 2 mixture amounted to about12%, i. e. abouhmonoohlorination. The chlorinated mixture .was'.distilled...in ivacuo rand the fraction whichdistilled betweens185 Duand 200 .C.;at" 5 mm. absolutetpressure-iwasscollected separately. :Itconsisted chiefly :of :the :monochlorinated'hydrocarbons.

A mixture of 600. parts of this. chlorinated. hy- I 'ldrocarbon.:mixture, .600 ;;parts tbenzoic sacid, and 200 parts sodium benzoatewas agitated and maintained between .230". and-240. (Lit-or. aboute2;hours andtthensdistilled in =vacuo. .'Ihe"fraction which distilledbetween 210and' 255..C.;at;'5;;m-m;;absolute pressure wascollectedsseparately. ;.It:consistedof. a neutral yellow viscous oil,.insolubleiin .water Land ..in :warmaa ueous pcaustic.-soda. ill;comprised chiefly kerosene .benzoate a (the There- :sene ,radicals.averaging; about. 19.nca1ibon; atoms) '183 :parts .101 1 the .ikerosenebenzoate rproduct -were 'mixed; with'83 parts .015 %':2.1Q0h01i0.-1$0111- tionof caustic soda, .and.the..-mixture"was-stirred and:heated under reflux to itslboiling 1 temperature for;.a'bout i2=hours.iThe mixture was then cooled. diluted with water zand thez-oilseparated.It was washed with water until the washings were neutral.100rparts:ctr-alight P6d: :0l1 .were thusobtained. 65 parts of this 1crude-soil :were .distilled. -About-=%- of-itdistilledbetweern 170 6:and'r220" .13.: atilzimm.'rabsc-luternressure :without apparentdecomposition.

ifilhe smixture :of ealcohols :ithus obtained :as a "lifihteyellowoil'rwasasulfonated with -io,e%; nisoiandmeutralizediwithcdilutecaqueous:causticcsoda,iyieldingzasoleargaqueouszsolution which possessed marked sdetergent:pro-perties. :The alcohols .rin the-mixture, like thezesters from whichthey-were Ederivedahadamarerage :carbon content .Dff aboutZBQQQar-bomatwns.

;Ea:umn1'e;.4.-:-:Kerosene which was -derivedrfrom:Bennsyluaniarpetroleumrwas distilledandtthe .dis- 2tillateiwhiehz-boilediibetween, 55 andi'751C.; at .115 mm. .iabsolute pressure wascollected separately. *Azportion-eof :this fraction-which,consisted'principally of 10 anditrl;carbonoatom hydrocarbons, waschlorinated with a direct-stream of chlorine in stherpresence/ of lightat axtemperature below 40 1C. runtil the organically combined chlorinetherein uarnounted i to about 19.3%. The chlo- :ri'natedimixturefthus'obtained was distilled in cache sand the ifraction which. distilledbetween 7-5za11d1125a0z'at15'mm. absolute pressure'rwas collectedseparately. It consisted largely of a mixture of monochlorinate'dhydrocarbonswhich -had-anaverage molecular carbon contentbe- Jtweenl 10;and i 11.

568 -partsof-stearic acid were melted and agitated :-at1'20 C. at'80parts of 50% aqueous caustic Soda-Were gradually added. Water wasallowed to distill oil as the caustic solution-wasadded. The mixture wasagitated and heated to -17 0"'C.==whi-1e a distillatetherefrom of 58parts of water was collected.

Tothisheatedmixture 185 parts of the-foregoing --monochlorinatedhydrocarbon distillate were added as the mixture was agitated, andmaintainedaha-temperature between 160 and l"7 0 C. The temperature ofthemixture was then gradually-raised to 215 ,C. over a period .of 1 /2hours and refluxedat about 215 C. for /2 hour longer. The mixtureboiledvigorously at this temperature. ,It-was-then'cooled to 200 C. anddistilled in vacuo. '91;parts,0f a mixture,,consisting chiefly ,ofolefine and chlorinated hydrocarb0ns,:.were.collecte'd as thedistillateboilingbelow. 150 "C. at 15mm. absolute pressure.

"The residue .Was transferred to an ,autoclaie. mixed with 420 parts .of14% aqueous caustic soda, and agitated-for about .16 hours..between 150and'l60'C. ,TIhe autoclave chargewas cooled .toiabout "50 C.. and .the.solid. mass was warmed w'ith;360,.parts ,of. aqueous. 10 hydrochloricacid solution. ..From the s1urry..300.parts of neutral aqueousssaltsolution were separated and the residue was distilledi-n acuo.Adistillate fractioniconsistingsof. about50 parts of oil andabout .400.partsof water .wascollected.before th temperature ofthe vapors from-the:distilling mixture exceeded 150 C. at 15 mm. absolute pressure. .Theoilwaaseparated from this distillate fraction and distilledsbetweenand.125" .C. .at 20mm. absolute pressure. .Theresultingdistillate ha d-.aispecific. gravity -:at..20/15=0.856. .It consisted chiefly iofaamixtureof alcohols. It wage-light :yellowaoil with {the odor-characteristic ofmoderately longechainfalcohols. It distilled ingsteam with-comparativeease-and was very slightly sol- .uble in -water. -It .-was. miscible inall proportions .with eethylealcohol, and practically insoluble i-ndilute-.aqueoussacid and alkali, :The oilzreacted :with %.H2SO4withevolution ofheatt form ;:a :dark: red-.iliquiid which, when drowned in:dilute aqueous: causticg formed sacclear solution of :the

7 alkylsodium sulfate which foamed readily when agitated and haddetergent properties.

Example 5.A distilled fraction of kerosene from Pennsylvania petroleumwas selected by boiling range comparison with known'hydrocarbons as amixture which consisted principally of 14 carbon atom hydrocarbons. Itwas chlorinated directly with chlorine gas in the presence of difi'usedlight until the organically combined chlorine was equal to that requiredtheoretically for monochlorination. The chlorinated mixture wasdistilled, and the fraction distilling between 130 and 155 C. at 18 mm.absolute pressure was collected separately as the desired mixture ofchlornated hydrocarbons which comprised chiefly the monochlorinatedcompounds.

568 parts stearic acid and 83 parts of a 50% aqueous caustic sodasolution were mixed and heated slowly to 170 C. to remove water, then232 parts of the foregoing chlorinated hydrocarbon distillate were addedin small portions over'a period of about 15 minutes while thetemperature' of the reacting mass Was maintained at about 190 C. Themixture was then heated under reflux to its refluxing temperature, i. e.about 215 to 220 C. for about 2 to 3 hours. .The mass was cooled anddistilled until a distillate of about 93 parts consisting chiefly ofchlorinated hydrocarbons was collected. (The last of this distillate wasobtained at about 165 C. at 24 mm. absolute pressure).

The distillation residue was cooled, transferred to an autoclave, mixedwith 300 parts water and 135 parts of 50% aqueous caustic soda, andheated and agitated under pressure at a temperature of about 150 toabout 160 C. for about 16 hours. The contents of the autoclave were thencooled and thoroughly mixed with 140 parts of B. hydrochloric acid and200 parts water. The mixture was heated and agitated under reflux untilthe whole mass was fluid, then it was cooled until the organic materialtherein became solid. The aqueous brine which separated from the solidwas removed and'the residual organic matter was distilled in vacuo. Thedistillate going off in the vapor temperature range of 130 to 165 C. at18 mm. absolute pressure was collected as the alcohol product. Itconsisted chiefly of aslightly turbid straw-yellow oil (specific gravityat 20/15=0.839), which separated from the water distillate and which wasinsoluble in dilute aqueous caustic soda. It had the odor commonlyassociated with long-chain alcohols and consisted of a mixture ofalcohols having an average molecular carbon content of 14. The mixtureof alcohols was. miscible in all proportions with kerosene and fairlysoluble in alcohol.

Example 6'.A fraction of kerosene from Pennsylvania petroleum. whichfraction had a boiling range of from 110 to 125 C. at 6 mm. absolutepressure and consisted of 14, 15, and 16 carbon atom hydrocarbons, waschlorinated directly with a stream of chlorine gas in the presence ofsunlight and at a temperature below 50 C, until the organically combinedchlorine therein was equal to about 13.9%, i. e. until the amount oforganically combined chlorine was substantially equal to that requiredif monochlorination of all the hydrocarbons in the mixture had beeneffected.

The chlorinated mixture was distilled in vacuo, and the fraction goingover at vapor temperatures from 125 to 145 C. at 6 mmjabsolute pressurewas collected separately. A mixture of 100 parts of this chlorinatedhydrocarbon distillate, 64 parts of dry sodium salicylate, and 100 partsof salicylic oil.

tale of common salt were'deposited as the formation of the esterproceeded. At the end of the heating period, the mixture was washed withdilute aqueous caustic and distilled in vacuo, and the fraction goingover at vapor temperature from 195 to 225 C. at 10 mm. absolute pressurewas collected separately. 7

The distillate fraction so collected was a neutral oil, insoluble inwater and in warm aqueous caustic. It comprised chiefly kerosenesalicylates (the kerosene radicals containing an average of 15 to 16carbon atoms), from which the alcohols could be obtained in the samemanner as described in connection with Example 1.

Example 7.A commercial aromatic extra-ct derived from petroleum wasidentified by boiling range comparison with known hydrocarbons as amixture which contained an average of about 12 carbon atom hydrocarbons.This product had a specific gravity at 24 C. of 0.862 and more than 50%of it Was soluble in concentrated sulfuric acid. It was chlorinateddirectly with chlorine gas in the presence of about 0.04% added iodineuntil the organically combined chlorine in the chlorinated mixture wasequal to about 106% of that required to be present theoretically if allthe hydrocarbon in the mixture were monochlorinated. The chlorinatedmixture was distilled, and the fraction distilling between and C. at 15mm. absolute pressure was collected separately as the desired mixturecomprising chiefly monochlorinated compounds.

100 parts of sodium benzoate and 500 parts of benzoic acid were agitatedand heated to 200 C. parts of the foregoing monochloride fraction werethen added gradually over /2 hour as the reaction temperature wasincreased to 220 C. Agitation was continued for 2 hours longer and thetemperature was maintained at 220 to 230 C. After being cooled to 170C., the turbid liquid was drowned in cold water and neutralizedby slowaddition to 50% aqueous caustic soda. The

' and filtered. The filtrate was washed with aqueous caustic soda ofabout 1% NaOH concentration and distilled. The residue boiling above C.at 15 mm. absolute pressure was taken as the desired kerosene benzoate.It was a dark viscous Saponification of a sample showed it to be 91%ester, calculated as a (C12) kerosene monobenzoate. The resulting oilwas dark brown and had a distinctly phenolic odor. A couplin test waspositive for phenolic bodies.

Example 8.A distilled fraction of kerosene from Pennsylvania petroleumwas selected by boiling range comparison with known hydrocarbons as amixture of hydrocarbons which contained between 13 and 14 carbon atomsper average molecule. t was chlorinated directly with chlorine gas inthe presence of about 0.04% added iodine until the organically combinedchlorine was equal to that required theoretically for about 120% of'monochlorination. The chlorinated mixture was distilled and thefraction distilling between 120? and 145 C. at 25 mm. absolute pressurewas collected separately as the desired mixture comprising chieflymonochlorinated comencased oi? estrs bf-benzoic acid; end-freeing *themixture of esters arom impurities by distillation; hereby a purified'rnixture'cf esters yielding the corre spendingmixtureofalcohols-uponhydrolysi'sis continued-'-for l2 hour s longer and thetempe'rafii'produ'ce'd;

ture maintained-atQZM- to 230 -'-'C.-- After cooling to -l60 01, theliquid: masswas quenched:-onxicei and neutralized with caustic soda.Aboutv 88 parts' of be-nzene Were-added' and'th' ower aaue In a processe of;preparing mixtures 1 of nee-- hols containing not rnore than asmallproportion of non-alcoholioinipurities, the steps which com--= prisereacting a mixture of chlorinated higher hy cue-layer was: withdrawnThenoil iwasewashed; 1% drocarbcnscontainingchlorinat'ed non aromaticonce with yery"dilute -caustic and then distilled: The fractiondistilling-between#1659132 at; :15 Imim; absolute pressure and-izofi Q--at 141mm; absolute pressure: was collected separately aS the'i desiredhaving practically noodors Sapon-ification' or tzas sample showed it tobe'l03.5 %'iest.er; calculatedsas I a" (013.5) kerosene monobenzoatewThe *alcoholJso obtained was a light yellow smobile oil having; an:

I claimw 1. A process of preparing .purifiedimixturesraof esters adaptedto be hydrolyzedttormixturesrof al cohols, which comprises condens-ingaa:mixture? of halogenated higher; hydrocarbons' l containing ihalogenated nonaaromatic; hydrocarbon :groups; with -a11salt= of azm'onocarboxyrlic acid': containing; not less than 6 carbon atoms in itsmolecule; the presence of as-fiuxicomprisingoal monocarboxrz ylic cidcontaining notiless athan =6 icarboncatomsr; in "its molecule; therebytformingr av mixture on; monocarboxyliclacid esters, land;freeingsthermix-t ture of esters from-impurities by distillation;

2.- In process; of:.prep aring 3 mixtures, of 3100: hols containingmotimore than .asmall proportion; ofnonalcoholic impurities, :thestepswhich com-j prise iscondensing a1 .mixtureaof halogenated hydrocarbo-nslcontainingihalogenated nonraromati il hydrocarbon-groups andb'etizsieenx 12- and- 19 car bon atoms per molecule with a salt ofaymonooar boX-yli'c acid .cont'ainingitnot:.less than 6 carbon atoms inits molecule in the presence of a flux comprising a monocarboxylicacidcontaining not less than 6 carbon atoms in its moleculatherebyforming a mixture of mo-nocarboxylic acidesters, and freeing the mixtureof esters from impurities by distillation; wherebya-purified mixture ofesters yielding the corresponding mixture oi alcoh ls: up eh lolysisisrre i a I a prcc ssnf. pr pa in mi u Oi-e em hols: containingnot, more than a small proportion of non alcoholic, impurities, the -steps whicn comeprise heating a mixture of chlorinated higher hydrocarbonscontaining chlorinated non-aromatic hydrocarbon groups with a; salt of amr1ocar Ylic atcidvcontaininezc t: Je sih bo atoms in tsmoleculein the,pr sen e of a flux comprising I amqnoqatbqxylic acidcontain-ing not lessthan 6 carbon atoms in its molecule, at a pressure suflicient tomaintain said chlorinated higher hydrocarbons in liquid phase atreaction temperature, thereby forming a mixture of monocarboxylic acidesters, and freeing the mixture of esters from impurities bydistillation at a pressure substantially below reaction pressure,whereby a purified mixture of esters yielding the corresponding mixtureof alcohols upon hydrolysis is produced.

4. In a process of preparing mixtures of alcohols containing not morethan a small proportion of non-alcoholic impurities, the steps whichcomprise reacting a mixture of chlorinated higher hydrocarbonscontaining chlorinated non-aromatic hydrocarbon groups with a salt ofbenzoic acid in a benzoic acid flux, thereby forming a mixture itsmolecule hydrocarbon group's-with a salt of stear-icgacid in astearicacid ilu thereby forming a mixtu're 0f esters o stearic acid; andfreeing-the-mixture of? esters from impurities-by distillation#whereby akerosene tga... It wasa iayellow; mcbil eoil-i gipurified mixture-oiesters yi'eldingthe correspond ing mixture' of I alc'ohol's uponhydrblysi's is 6: eaprocessior prep aringImixtures' ofalco-= hols:containin'g not rnore than: a small proportion w odor typical oin-the:longschainllaliphaticaalcoholsa; 03.10f'4101'12d00h01i0-impllritiS, -thesteps-which com prise-re'acting'a mixture ofchlorinated higher hy 1drccarbons containing chlorinatedcnomaromatichydrocarbon; groupswithraasaltuof salicylic acid in a salicylic: acid flux; therebyiforming a mix ;ture of estersof salicylic: acid; and afreeing-Jthmixture .015; estersofrom impurities by-tdistiHatiorr; wher ebyia-lzpurified-amixturetof esters/yielding Lthe correspondingflmixture ofalcohols upon hydrolye sis Lia-produced:

of noni.

esters i l echo au or rcl vo rsis i ,.rirmiuq a m xtur spf aloe-e 1s;'.n einins:;- 0t m t n. ro -no e phclic imn e i e mpri rh se am ra e. 41.3 y sesame-exercise:me esulers r e t11 sth m l -w a sa ie tonoca q racid cont ng. no v m etut iq -m eta bex acide e a hols? not more"r,lri'an {a ism-all: proper; tion vpr non-alcoholic, impurities, lthesteps which.

-Pr se h a l .v y C. and 275 Cfa halogenated "petroleum distillateconsisting mainly of monohalogenated hydrocarbons containing between 12and 19 carbon atoms per molecule with a salt of a monocarboxylic acidcontaining not less than 6 carbon atoms in its molecule in a flux ofsaid acid, thereby forming a mixture of monocarboxylic acid esters, anddistilling off impurities from the mixture of esters, whereby a purifiedmixture of esters yielding the corresponding mixture of alcohols uponhydrolysis is produced.

10. In a process of preparing mixtures of alcohols containing not morethan a small proportion of non-alcoholic impurities, the steps whichcomprise heating at a temperature between C.

and 275 C. a kerosene chloride consisting mainly h l enated n t! m d tila e: f

, -t amficarbona as 'n a flux of said acid, thereby form:

g at temperature tween 150 l tween 12 and 19 carbon atoms permoleculewith an alkali-metal salt of a monocarboxylic acid containingnot less than 6 carbon atoms in its molecule in a flux of said acid,thereby forming a mixture of monocarboxylic acid esters, and distillingoii impurities from the mixture of esters,

whereby a purified mixture of esters yielding the corresponding mixtureof alcohols upon hydrolysis is produced. 7

11. Aprocess of preparing a purified mixture of esters adapted to behydrolyzed to a mixture ing at a temperature between 150 C. and 275 ofmonohydroxy alcohols, which comprises heat- C. a chlorinated petroleumdistillaterconsisting' 15 carbons containin between .12 and 19 carbonatoms per molecule with an alkali-metal salt of V essentially ofmonochlorinated saturated hydrobonatoms in its molecule in a flux ofsaid acid,

thereby forming a mixture of esters of the carboxylic acid, anddistilling oif impurities from the mixture of esters.

pheric pressure, thereby forming a. mixture of esters of thestearic-;acid, subsequentlyreducing the pressure on said mixture ofesters and distilling off impurities from the mixture of esters.

- 15. An improved process for preparing a mixture of monocarboxylic acidesters, which comprises condensing a mixture of halogenated higherhydrocarbons containing halogenated non-aromatic hydrocarbon groups witha salt of a monocarboxylic acid containing not less than 6 carbon atomsin its molecule, in the presence of v a flux comprising a monocarboxylicacid containing not a monocarboxylic acid containing at least 6 carr 12.A process of preparing a purified mixture i of monohydroxy alcohols,which comprises reof esters adapted to be hydrolyzed to a mixture actinga chlorinated petroleum distillate consisting essentially ofmonochlorinated saturated hydro'carbons containing between 12 and 19carbon atoms per molecule with sodium'benzoate in the presence of abenzoic acid flux at a'temperature between 150 C. and 275 C. and aboutat- 1 mospheric pressure, thereby forming a mixture distilling oilimpurities therefrom.

of esters of the benzoic acid, subsequently reduc- 7 .ing thepressure'on said mixture of esters and 13. A'proce'ssof preparing apurified mixture of esters adapted to be hydrolyzed to a mixture ofmonohydroxy alcohols, 'Vwhich comprises reacting a chlorinated petroleumdistillate consisting essentially of monochlorinated saturatedhydrocarbons containing between'12 and 19 carbon 7 atoms per moleculewith sodium salicylate in thepresence' of a salicylic acid flux at atemperature; between 150 C'. and 275 C. and about 'atmospheric pressure,thereby forming a mixture of esters of the salicylic acid, subsequentlyreducing the-pressure on said mixture of esters and distilling offimpurities from the mixturegof "es-u ters. V a V 14. A process ofpreparing a purified mixture of esters'adapted to be hydrolyzed to amixture acting a chlorinated petroleum 'distillateconsisting essentiallyof monochlorinated saturated hydrocarbons containing between 12 and 19carbon atoms per moleculewith sodium 'stearate in the presence" of'stearic' acid flux at a temperature between 150 C. and 275 and aboutatmosof monohydroxy alcohols, whichcomprises reless than 6 carbon atomsin its. molecule. F

16. A process for preparing a mixture of monocarboxylic acid esters of,phenols and of. alco-. hols, which comprises. condensing a mixture ofhalogenated higher hydrocarbons containing halogenated, aromatic andnon-aromatic hydro 7 r 7 carbon groups with a salt of, a monocarboxylic,acid containing not less than 6 carbon atoms in i its molecule, in thepresence of a fiux comprising a monocarboxylic acid containing not lessthan 6 carbon atoms in its molecule,

17. In a process of preparing mixturesof alcoholsand phenols containingnot more than a small proportion of non-alcoholic and non-phenolicimpurities, the steps" which comprise con-7, densing a, mixture ofhalogenatedhigher hydro-- carbons containing halogenated, aromatic and Vnon-aromatic hydrocarbon groups'with a ,salt of' .a monocarboxylic acidcontaining not less than; 7

6 carbonatoms in'its molecule in the presence of a flux comprising amonocarboxylic acid'cone f V tainingjnot less than 6 carbon atoms in itsmolecule, thereby formingla mixture of monocarboxylic acid esters andfreeing the mixture of esters from impurities by distillation, whereby apurie fied mixture of esters yielding the correspondling- 1 mixture ofalcohol s and phenols'upon hydrolysis isproduced.

1 REF RENCES CITED 7 The following references are of record in the*fil'e of this patent:

ZUNITED STATES PATENTS MICHAEL EI'I'ELMAN} 1 7 Germany r Oct. 19, 1911-:

Certificate of Correction Patent No. 2,428,450. October 7, 1947.

MICHAEL A. EITELMAN It is hereby certified that errors appear in theprinted specification of the above numbered patent requiring correctionas follows: Column 2, line 23, for 160 C. read 165 0.; column 6, line29, for at 80 read as 80 column 7, line 15, for chlornated readchlorinated; column 12, line 38, for correspondling read corresponding;and that the said Letters Patent should be read with these correctionstherein that the same may conform to the record of the case in thePatent Office.

, Signed and sealed this 2d day of December, A. D. 1947.

THOMAS F. MURPHY,

Assistant Commissioner of Patents.

